Method of producing halogenated phenoxy-s-triazines

ABSTRACT

Production of halogenated phenoxy-s-triazines by the reaction of halogenated phenols and C-chlorides of s-triazines in the presence of catalytic quantities of tertiary amine or carbonamide compounds or quaternary ammonium salts thereof.

I United States Patent 1151 3,682,908

Ismail 1 51 Aug. 8, 1972 54] METHOD OF PRODUCING HALOGENATED PHENOXY-S-[56] References Cited TRIAZINES UNITED STATES PATENTS [72] Inventor:Roshdy Ismanl,Sp1ch,Germany 3 049 S42 8/1962 R a] 260,248

ose et [73] Tmsdmf (Bel 3,407,201 10/1968 Luethi et al. ..260/248 g y3,415,824 12/1968 Biland et a] ..260/248 [22] Flledz May 5, 1970 [21]App], No,; 34,900 Primary Examiner.lohn M. Ford Attorney-Burgess,Dinklage & Sprung Related US. Application Data [63] Continuation of Ser.No. 737,129, June 14, [57] ABSTRACT 1968' abandoned Production ofhalogenated phenoxy-s-triazines by the reaction of halogenated phenolsand C-chlorides of s- [30] Fomgn Apphcafio Monty triazines in thepresence of catalytic quantities of terti- June 15, 1967 Germany ..D53345 ry amine 0r carbonamide compounds or quaternary ammonium saltsthereof. [52] US. Cl. ..260/248 CS [51] 1111, C1. ..C07d ss/so Claims![58] Field of Search ..260/248 CS METHOD OF PRODUCING HALOGENATEDPHENOXY-S-TRIAZINES This application is a continuation of applicationSer. No. 737,129, filed June 14, 1968, now abandoned.

The object of the present invention is a method of producing halogenatedphenoxy triazines from halogenated monohydric phenolic compounds and C-chlorides of s-triazine. The method is particularly characterized by thefact that the C chlorides of the triazines are reacted with thehalogenated monohydric phenolic compounds in the presence of catalyticquantities of tertiary amines whose amino group may possibly be a partof an aromatic ring system, and/or possibly N-monoor -disubstituted acidamides, possibly in solvents, at a temperature of 50-2 50 C andpreferably 80-200 C.

The preparation of phenyl esters of halogenated phenols of cyanuricchloride is described in J. Am. Chem. Soc. 73, 1959, pp 2992 et seq. Thepreparation is based on the reaction of cyanuric chloride with thealkali salts of the halogenated phenols in acetone-aque ous medium. Thedisadvantages of this method are as follows:

l. The use of large quantities of alkali;

2. After termination of the reaction, the final product must be washedout with large quantities of water in order to completely remove NaCl;

3. The drying of the final product requires a long drying time forcomplete removal of the water;

4. Furthermore, this reaction is also very incomplete so that largequantities of unreacted starting compounds must thereupon be separatedfrom the final products.

It is, therefore, an object of this invention to provide an improvedmethod of producing halogenated phenoxy-s-triazines.

It is another object of this invention to provide an improved catalystfor the reaction of halogenated phenols with C-chloro-s-triazines.

Other and additional objects of this invention will become apparent froma consideration of this entire specification, including the claimshereof.

In accord with and fulfilling these objects, one aspect of thisinvention is the improvement in the reaction of halogenated phenols withC-chloro-s-triazines to produce.halophenoxy-s-triazines by catalysis ofsuch reaction with tertiary amines, acid amines, or quaternary ammoniumsalts thereof.

It has been found that the disadvantages noted above can be avoided inaccordance with the present invention by carrying out the method for thepreparation of halogenated phenoxy-s-triazines in the manner that theC-chlorides of the s-triazine are reacted with the halogenatedmonohydric phenolic compounds in the presence of catalytic quantities oftertiary amines whose amino group may be a part of an aromatic ringsystem, and/or possibly N-monoor -disubstituted acid amides, possibly ininert solvents, at temperatures of 50250 C and preferably of 8U200 C.The chlorides of s-triazine and their derivatives react surprisinglyreadily with halogenated phenolic compounds, splitting off HCl, in thepresence of catalytic quantities of the said tertiary amines, etc. Inthe same manner as the tertiary amines, and possiblyN-monoor-disubstituted acid amides, there are also useful as catalyststhe quaternary salts thereof with hydrochloric acid, acetic acid,halogenated phenolic compounds, etc.

The reaction in accordance with the present invention is preferablycarried out at normal, e.g. atmospheric, pressure. However, it can alsobe carried out at a pressure of up to about 12 atmospheric gauge.

For the preparation of the halogenated phenoxy-striazines, theC-chlorides of s-triazine and the halogenated phenols are preferablyused in stoichiometric ratio, i.e., 1 mole of halogenated phenol is usedper mole of s-triazine chloride. However, higher or lower ratios can beprovided, if desired.

For the carrying out of the method in accordance with the inventionthere are suitable individual and mixed tertiary amines havingaliphatic, cycloaliphatic and aromatic radicals or their mixtures, inwhich connection substituted imines are to be understood in accordancewith the present invention as within the meaning of cyclic tertiaryamine. Exemplary tertiary amines having aliphatic radicals are, forinstance, trimethylamine, triethyl-amine, triisopropylamine,triisobutylamine, monoethyl diisopropyl-amine,monoethyl-di-n-butylamine, tri-n-butylamine, N,N,N',N'-tetramethylbutane diamine-(l,4), and N,N,N',N'-tetramethyl ethylene diamine. Alsoincluded are tertiary, aliphatic amines containing heterosubstituents.These are exemplified by B-chlorpropyl di-propylamine, tris-(B-ethoxyethyl)-amine,

methylaminoacetonitrile, N,N-di-n-butylaminoacetonitrile, N,N-diisopropylaminoacetonitrile, N,N-butyl-N- methylaminoacetonitrile,methyleneaminoacetonitrile, N,N-diisobutylaminopropionitrile,fi-dirnethylaminoproprionitrile, dimethylaminoacetonitrile, anddimethyl-p-aminobenzonitrile. From the group of amines withcycloaliphatic radicals, N,N-dimethyl cyclohexylamine can be mentionedas example. Furthermore, other suitable amines with aromatic radicalsare included, such as N,N-dialkylaniline (N,N-dimethylanilin, N,N-diethylaniline, etc.), p-bromophenyl dimethylamine, 2,4-dinitrophenyldi-methylamine, benzyl dimethylamine, p-nitrophenyldi-n-butylamine,N-(2,4- dichlorphenyl)-diethylamine, N,N,N',N'-tetramethyl benzidine,etc. Suitable heterocylcic tertiary amines are, for instance, N-alkylorN-aryl-morpholines, such as N-n-butylmorpholine, N-phenylmorpholine,N-(pmethylphenyl)-morpholine, morpholinoacetic acidmorpholide; N-arylorN-alkyl-tetrahydroquinolines, or tetrahydroisoquinolines, such asN-n-propyltetrahydroquinoline, N-phenyLtetrahydroisoquinoline;N-alkyland N-aryl-pyrrolidines and their derivatives, for instance,N-methyl-pyrrolidine, N-n-butyl-pyrrolidine, N-phenyl-pyrrolidine, etc.Aromatic tertiary amines are furthermore exemplified by pyridine,isoquinoline, pyrazine, oxazine, quinazoline, oxazol, oxdiazol,benthiazol, etc. Tertiary amines which additionally contain at least onenitrile group have proven particularly suitable for the carrying out ofthe method of the present invention.

N-monoor -disubstituted acid amides useful in this invention areexemplified by those which are the carbonamides of monobasic aliphatic,aromatic and araliphatic carboxylic acids having about one to 18 carbonatoms. The said monobasic acids, such as formic acid, acetic acid,propionic acid, butyric acid, caproic acid, Z-ethyl-hexanoic acid,caprylic acid, lauric acid, palmitic acid, stearic acid, benzoic acid,phenylacetic acid and phenyl-butyric acid may be straight-chained orbranched or have the alkyl chain interrupted also by a keto group, suchas in pyruvic acid, acetoacetic acid or levulic acid. The amine part ofsuch amides are exemplified by ammonia or monoor diamines. There arepreferred primary or secondary monoor diamines which are derived fromthe saturated aliphatic, araliphatic, cycloaliphatic series or from thearomatic series with only one aromatic ring. By way of example, mentionmay be made of such amines as methylamine, dimethylamine, di-nor-i-propylamine, di-nor -isobutylamine, di-2-methyl-hexylamine,dilaurylamine, ethylene diamine, tetramethylene diamine, hexamethylenediamine, cyclohexylamine, dicyclohexylamine, benzylamine, dibenzylamine,aniline, methylaniline, toluidine, phenylene diamine andhexahydrophenylene diamine. One or both alkyl groups of the amines canalso be replaced or substituted by the phenol or toluyl radical or bycycloalkyl groups having about five to six ring carbon atoms, whichgroups or rings may possibly further be substituted by alkyl groups, andparticularly one or two methyl groups. Of the diamines which areparticularly suitable as amine component for the preparation of the acidamides of this invention there may be mentioned in particular those inwhich the amine groups are separated by about one to 8 methylene(including aromatic CH) groups. in the case of the diamines also, thehydrogen atoms still bound to the nitrogen atom can be replaced, exceptfor at least one thereof, for instance by alkyl groups having about oneto four carbon atoms, a phenyl or toluyl radical or a 5- to 6-membercycloalkyl radical. As representatives of particularly suitablecarbonamides which are used as catalysts in accordance with theinvention, the following may, in particular, be mentioned:

Formamide, methylformamide, dimethylformamide, diethyl-formamide,acetamide, N,N-dimethylacetamide, N,N-di-nor -i-propyl-butyramide,N,N-di-nor isobutylbutyramide, N-benzyl-butyric acid amide, N,N-dipropylethyl hexanoic acid amide, acetoacetic acid-N,N-di-n-butylamide, acetoacetic acid anilide, benzoic acid benzylamide,N,N-dimethyl benzoic acid amide and N,N'-diformyl hexamethylene diamine.Cyclic acid amides or imides can also be used.

Barbituric acids, unsubstituted or which may be substituted byhydrocarbon radicals, particularly by methyl-bis-nor -isobutyl or phenylgroups, such as dimethyl barbituric acid, diethyl barbituric acid,dipropyl barbituric acid, diallyl barbituric acid, di-nbutyl barbituricacid and phenylethyl barbituric acid have been found to be usefulcatalysts for this reaction.

It is not necessary to use preformed amides directly as the catalyst forthis reaction. Alternatively, the catalyst amide can be formed in situby adding the components from which they are synthesized. For instance,a mixture of a primary or secondary monoor diamine of the aforementionedtype and one of the said monocarboxylic acids or the acid chlorides oranhydrides derived from said acids can be added to the reaction mixturesince the desired catalytic acid amides are then formed under thereaction conditions.

Sulfonamides, such as 4-sulfamoyl-acetaniline, N'- amidino-sulfanilamideand N-2-pyridyl-sulfanilamide are also suitable catalysts.

Phosphorous acid amides, such as hexamethyl phosphorous acid amide,hexamethyl phosphoric acid amide, hexa-n-butyl phosphorous acid amide orhexaisobutyl phosphorous acid amide, phosphorous acid trimorpholide canalso be used as catalysts. Phosphoric acid triamides can also beemployed as catalysts, but their catalytic effect is somewhat inferiorto that of phosphorous acid amides.

Titanic acid amides and stannic acid amides, such as di-propoxy titaniumdiamide and di-n-isobutyl tin diamide or di-isobutyl tin diamide canalso be used as catalysts.

Mixtures of the aforementioned tertiary amines and acid amides can, ofcourse, also be used as catalysts.

The tertiary amines and acid amides employed as catalysts are used inquantities of (Ll-20 mol percent and preferably 0. l-2 mol, referred tothe moles of the triazine chloride.

Under the conditions in accordance with the invention, the condensationtakes place rapidly with the separation of practically stoichiometricquantities of gaseous HCl. This advantage is shown by the followingcomparison of two experiments:

The reaction of pentachlorophenol, with cyanuric chloride in xylenetakes place so slowly that only about 10% HCl is split off within 24hours. Under the same reaction conditions, in the presence of tertiaryamines as catalysts, about 98% HCl is split off within the first 3 hoursof reaction.

The reaction should be carried out in the liquid phase. This includesboth molten reaction mixture and solutions. The inert solvent can beeither a true solvent and a dispersant medium. Suitable solvents withinthe meaning of the present invention are those which are substantiallyinert both to the reactants and reaction product under the reactionconditions. These include both aliphatic and aromatic hydrocarbons,substituted hydrocarbons and linear or cyclic ethers are also useful. Asaliphatic hydrocarbons there may be mentioned both individual compoundsand mixtures thereof, such as isooctane and benzene fractions, forinstance those having a boiling range of l20-200 C. Cycloaliphaticcompounds, such as decahydronaphthaline can also be used. Benzene,toluene, xylene, o-dichlorbenzene and nitro-benzene are examples ofsuitable aromatic solvents. As esters which are suitable for thecarrying out of the reaction, mention may be made of diisopropyl ether,diisoamyl ether, dimethyl ethers of ethylene or diethylene glycol,diphenyl ether, 1,4-dioxan, etc. The above list of suitable ethers showsthat both open chain and cyclic ethers can be employed. Polar solvents,such as dimethyl sulfoxide and dimethyl formamide can also be used.

As the aromatic reactant for the carrying out of the method of themethod of the invention, there are suitable halogenated, monohydricphenolic compounds which can be generally referred to as phenols. Thesephenols may have alkyl, particularly lower alkyl, sub stituents thereon.

Suitable halogenated monohydric phenolic compounds are, for instance,the fluorinated phenols, such as 4-fluorophenol, pentafluorophenol, thechlorinated phenols, such as 2-, 3, 4-chlorophenols, 2,3-, 2,4-, 2,5-2,6-, 3,4-, 3,5- dichloro-phenols, 2,4-dichloro-6- methylphenol,2,6-dichloro-4-tert.-butylphenol, 2,3,5-, 2,4,5- and2,4,6-trichlorophenols, 2,3,4,6- tetrachlorophenol, as well aspentachlorophenol, the brominated phenols, such as 2-, 3-,4-bromophenols, 2,4-, 2,6-dibromophenols, 2,4,6-tribromophenol andpentabromophenol, and the iodated phenols, such as 2,4-,2,6-diiodophenols and 2,4,6-triiodophenol. However, halogenatednaphthols and heterocycles of a phenolic character can also be used,such as l-hydroxy- 2,4-dibromonaphthaline and 8-hydroxy-5,7dibromoquinoline. In addition to alkyl groups, the said monohydricphenolic compounds can also bear alkoxy, carboxy, and phenoxy groups assubstituents. Of course, mixtures of the said halogenated phenols canalso be used in accordance with the invention.

The trizine reactants used in accordance with the invention arecompounds which are derived from the following basic substance:

ln this basic substance, at least one hydrogen atom is replaced by achlorine. However, up to 3 hydrogen atoms can be replaced by chlorine.One or two hydrogen atoms can be furthermore replaced by identical ordifferent amine radicals of the following general formula:

and/0r aryloxy radicals, e.g. lower alkoxy.

In this formula:

R can be hydrogen or an alkyl or cycloalkyl radical, possiblyhalogenated,

R can be an alkyl or cycloalkyl radical, possibly halogenated, or anaryl radical,

And R and R can also jointly be a member of a heterocyclic ring system.

Suitable C-chlorides of s-triazine are, for instance, cyanuric chloride,2-anilido-4,6-dichloro-s-triazine,2,4-di-(di-ethylamino)-6-chloro-s-triazine,2-n-butylamino-4,6-dichloro-s-triazine, 2-cyclohexylamino-4,6-dichloro-s-triazine, 2-n-octyl-amino-4,6-dichloro-striazine,2-morpholino-4,6-dichloro-triazine,2-ethoxyethylamino-2,4dichloro-s-triazine, 2-piperidino-2,4-dichloro-s-triazine, and 2-a-naphthylamino-2,4- dichloro-s-triazine,etc.

The compounds prepared in accordance with the invention, in view oftheir fire-retarding, fungicidal, phytotoxic, bactericidal and in partalso insecticidal properties, can also be used as water-repellingagents, parting agents, sizes for glass fabrics, textile adjuvants andfor surface treating agents.

Various embodiments of the method of the invention are illustrated bythe following examples.

EXAMPLE 1 2-anilido-4,6-di-(pentachlorophenoxy)-s-triazine In athree-neck bottle provided with agitator, condenser and feed tube, 24.lg of 2-aminido-4,6-dichloros-triazine and 53.3 g of pentachlorophenolare reacted in 300 ml of xylene in the presence of 0.5 g ofN,N-di-nbutylaminoacetonitrile. The reaction mixture was stirred at theboiling point of the toluene. The HCI gas produced was flushed by meansof nitrogen out of the reaction mixture and collected in NaOH solution,which was titrated after the conclusion of the reaction. The reactionwas complete within about 24 hours.

The product was obtained in the from of a white crystalline material ina practically quantitative yield. M.p.: 260-264 C.

Theoretical Found C: 35I99% 36.64% H: 0.86% 0.82% N: 7.99% 7.77% CI:50.7% 49.3%

EXA M PLE 2 2-chloro-4,6-di-(2,3 ,4,6-tetrachlorophenoxy )-striazine Ina threemeck bottle provided with agitator, con denser and droppingfunnel, 92.2 g of cyanuric chloride and 231.9 g of2,3,4,6-tetrachlorophenol were reacted in [,200 ml of xylene with 1.5 gof N-methylpyrrolidine. The reaction mixture was stirred at the boilingpoint of the xylene. The HCl gas produced was flushed out of thereaction mixture by means of nitrogen and collected in NaOH solution.The reaction was complete in about 8 hours. The product was a whitecrystalline substance. M.p.: 235C. Yield: about percent.

Theoretical Found C: 31 3% 30.1% H: 0.34% 0.50% N: 7.29% 7.20% Cl: 55.5%54.9%.

EXA M PLE 3 2-chloro-4,6-di-(2,4,5-trichlorophenoxy)-striazine [n athree-neck bottle provided with agitator, condenser and dropping funnel,82 g of cyanuric chloride and 176 g of 2,4,S-trichlorophenol werebrought together in 1,000 ml of xylene with [.0 g of morpholinoaceticacid morpholide.

The reaction mixture was stirred at the boiling point of the xylene.

The HCI gas produced was flushed by nitrogen out of the reaction mixtureand collected in NaOH solution. After completion of the liberation ofthe HCI, the reaction mixture was filtered off. The product was a whitecrystalline material. M.p.: l89190 C. Yield: 97 percent.

EXAMPLE 4 2-chloro-4,6-di-( pentachlorophenoxy )-s-triazine In athree-neck bottle provided with agitator, condenser and feed tube, I844g ol'cyanuric chloride and 53.3 g of pentachlorophenol are reacted in300 ml of xylene with 0.5 g of tri-n-butylamine. The reaction mix-Theoretical Found 27.95% 27.55% N: 6.52% 6.53% CI: 60.6% 59.88%

EXAMPLE 2-chloro-4,6-di-( 2,4 ,o-tribromophenoxy)s-triazine in athree-neck bottle provided with agitator, condenser and dropping funnel,18.44 g of cyanuric chloride and 66.16 g of 2,4,6-tribromophenol weremixed in 300 ml of xylene with 0.5 g of N,N- dimethylaniline.

The reaction mixture was stirred at the boiling point of the xylene.

The HCI gas liberated was flushed by means of nitrogen out of thereaction mixture and collected in NaOH solution. After completion of theliberation of the HCl, the reaction mixture was filtered off. The crudeproduct was obtained in the form of a white crystalline material inalmost quantitative yield. M.p.: 176-200" C. Recrystallized from benzene(boiling range 150-165C). M.p.: 200204C.

EXAMPLE 6 2,4-di-(diethylamine)-6-pentachlorophenoxy-s-triazine in athree-neck bottle provided with agitator, condenser and feed tube, 19.79g of 2,4-di-(diethylamine o-chloro-triazine in 0.5 ml oftri-n-butylamine and 20.4 g of pentachlorophenol in 300 ml of toluenewere brought together. The reaction mixture was stirred at the boilingpoint of the toluene.

The HCl gas liberated was washed by means of nitrogen from the reactionmixture and collected in NaOH solution. The reaction was complete inabout 24 hours. The toluene was completely removed and the stickyresidue was stirred with a small amount of pentane, whereupon the masscrystallized. M.p.: l07-112 C. Recrystallized from cyclohexane: M.p.:117-119 C.

EXAMPLE 7 2-n-butylamine-4,6-di-(pentachlorophenoxy)-striazine in athree-neck bottle provided with agitator, condenser and feeding tube, 22g of 2-n-butylamine-4,6- dichloro-s-triazine, 53 g of pentachlorophenoland 0.5 ml of N,N-diisobutylaminoacetonitrile were reacted in 300 ml ofxylene. The reaction mixture was stirred at the boiling point of thexylene. The HCl gas liberated was flushed out of the reaction mixture bymeans of nitrogen.

The reaction was complete in about 20 hours. The precipitate which hadformed was filtered off. M.P.: 240-24 1 C.

Calculated Found C: 33.7% 33.5% H: 1.48% 1.6%

N: 8.3% 8.1% CI: 51.7% 51.3%

EXAMPLE 8 In a manner similar to Example 1, 24.1 g of2-anilido-4,6-dichloro-s-triazine, 53.3 g of pentachlorophenol were reacted in thepresence of N,N-di-n-butylbenzoamide as catalyst. The reaction wascomplete in about 24 hours. The precipitated product had a m.p. of 262C; yield: 96 percent.

EXAMPLE 9 In a manner similar to Example I, 92.2 g o-fcyanuric chlorideand 231 g of tetrachlorophenol and 1.5 g ofN,N,N',N'-tetra-n-butyladipic acid amide as catalyst were reacted. Theproduct which precipitated out had an m.p. of 235 C, yield: 97 percent.

EXAMPLE 10 [n a manner similar to Example 4, 18.44 g of cyanuricchloride, 53.3 g of pentachlorophenol and 0.5 g of N,N-di-n-propylhexanoic acid amide as catalyst were reacted. The product whichprecipitated had an m.p. of 325 C; yield: 92 percent.

EXAMPLE 1 1 In a manner similar to Example 4, 18.4 g of cyanuricchloride, 53.3 g of pentachlorophenol, and 0.5 g of hexamethylphosphorous acid amide as catalyst were reacted in 300 ml of xylene.After completion of the liberation of HCl, the product deposited in theform of a white precipitate. M.p.: 322 C; yield about percent.

EXAMPLE 12 in a manner similar to Example 3, 41 g of cyanuric chloride,88 g of 2,4,6-trichlorophenol and 0.5 g of methylene aminoacetronitrileas catalyst were reacted. After termination of the liberation of HCI,the reaction mixture was filtered off; the product melts at 188 C; yieldabout 90 percent. The attached drawing illus trates the liberation ofHCI in relation to time of reaction of 18.4 g of cyanuric chloride and53.3 g of pentachlorophenol in 200 ml of boiling xylene without acatalyst (curve 1); in the presence of 1 percent of weight ofN,N-di-n-butyl benzoic acid amide (curve 2); of 1 percent of weight ofbenzamide (curve 3); ofl percent of weight of methylaminoacetonitrile(curve 4); of 1 percent of weight of N,N-dimethylaniline (curve 5); of 1percent of weight of N,N,N', N, N", N"hexamethyl phosphorous acid amide(curve 6); of 1 per cent of weight of tri-n-butylamine (curve 7); and of1 percent of weight of pyridine (curve 8). The curves 2 to 8 demonstratethe technical advance achieved by the catalysts used according to theinvention.

What is claimed is:

1. [n the process of producing halogenated phenoxys-triazines by thereaction of halogenated phenols with C-ehloro-s-triazines in the liquidstate at temperatures of 50 to 250 C; the improvement which comprisescatalyzing said reaction with 0.1 to 20 mol percent, based upon thetriazine reactant, of a member selected from the group consisting offormamide, methyl formamide, dimethyl formamide, acetamide, N,N-dimethylacetamide, propionic acid amide, butyric acid amide,

N,N-di-n-propyl-butyramide, N,N-di-isopropyl-butyramide, N,Ncdi-n-butylbutyramide, N,N-di-isobutyl butyramide, N-benzyl butyramide,N,N-dipropyl-2-ethyl hexanoamide, caproamide, 2-ethyl hexanoamide,caprylamide, acetoacetic acid-N,N-di-n-butyramide, acetoacetic acidanilide, benzoic acid benzylamide, lauramide, palmitamide, stearamide,benzoamide, phenylacetamide, pyruvamide, acetoacetamide, levulamide,N,N-dimethyl benzoamide, N,N-di-formyl hexamethylene diamine, dimethylbarbituric acid, diethyl barbituric acid, dipropyl barbituric acid,diallyl barbituric acid, di-n-butyl barbituric acid, phenylethylbarbituric acid, triethyl amine, trimethylamine, triisopropylamine,triisobutylamine, monoethyl diisopropyl amine, monoethyl-di-n-butylamine, tri-n butylamine, N,N,N',N'-tetramethyl butane diamine- (L4),N,N,N',N'-tetramethyl ethylene diamine, fichloro-propyl di-propylamine,tris-(B-ethoxyethyU- amine, methyl amino acetonitrile, N,N'di-n-butylaminoaceto nitrile, N,N-diisopropylamino acetonitrile,N-n-butyl-N-methyl-amino-acetonitrile, methylene aminoacetonitrile,N,N-diisobutyl amino propionitrile, B-dimethylamino propionitrile,dimethylamino acetonitrile, dimethyl-p-amino-benzonitrile, N,N-dimethyl-cyclohexylamine, N,N-dimethyl aniline, N,N- diethyl aniline,p-bromophenyl dimethylamine, 2,4- dinitrophenyl dimethyl amine, benzyldimethyl amine, p-nitrophenyl-di-n-butyl amine,N-(2,4-dichlorophenyl)-diethyl amine, N,N,N,N'-tetramethyl benzidine, N-n-butyl morpholine, N-phenyl-morpholine, N-(pmethyl phenyl)-morpholine,morpholine acetic acidmorpholide, tetrahydroisoquinoline,N-n-propyltetrahydro-quinoline, N-phenyl-tetrahydro isoquinoline,N-methyl'pyrolidine, N-n-butylpyrrolidine, N phenyl-pyrrolidine,pyridine, isoquinoline, pyrazine, oxazine, quinazoline, oxazol,oxadiazol, benzothiazol, hexamethyl phosphoric acid amide, hexa-n-butylphosphorus acidamide, hexa-isobutyl phosphorous acid amide, phosphorousacid trimorpholide, diisopropoxy titanium diamide, di-n-butyl tindiamide, diisobutyl tin diamide, 4-sulfamoyl acetaniline,N-amidinosulfanilamide, N-2-pyridyl-sulfanilamide and quaternaryammonium salts thereof.

2. The improved process claimed in claim 1, carried out at a temperatureof about 80 to 200 C.

3. Improved process claimed in claim I, carried out at pressure of aboutatmospheric to about l2 atmospheres gauge.

4. Improved process claimed in claim I, wherein said catalyst is presentin a proportion of about 0.l to 2 mol percent.

5. lmproved process claimed in claim 1, wherein said reaction is carriedout in a solvent.

6. Improved process claimed in claim 1, wherein said reaction is carriedout in the melt,

7. Improved process claimed in claim 5, wherein said solvent is a memberof the group consisting of isoactane fractions having a boiling range ofabout to 200 C, benzene fractions having a boiling range of about l20 to200 C benzene, toluene, xylene, odichlorobenzene, nitrobenzene,diisopropylether, diisoamylether, dimethylether of ethylene glycol,dimethyl ether of diethylene glycol, diphenyl ether l,4 dioxane,dimethyl sulfoxide and dimethyl formamide.

8. Improved process claimed in claim 1, wherein said halogenated phenolis monohydric, I

9. mproved process claimed in claim I, wherein said halogenated phenolis a member selected from the group consisting of 4-fluorophenol,pentafluorophenol, 2-chlorophenols, 3-chlorophenols, 4-chlorophenols,

2,3-dichlorophenols, 2,4-dichlorophenols, 2 ,5- dichlorophenols,2,6-dichlorophenols, 3,4-dichlorophenols, 3,5-dichlorophenols,2,4-dichloro- Gmethylphenol, 2,6-dichloro-4-tert.-butylphenol,2,3,5-trichlorophenols, 2,4,5trichlorophenols, 2,4,6- trichlorophenols,2,3,4,6-tetrachlorophenol, pentachlorophenol, 2-bromophenols,3-bromophenols, 4 bromophenols, 2,4-dibromophenols, 2,6- dibromophenols,2,4,6-tribromophenol, pentabromophenol, 2,4-diiodophenols, 2,6diiodophenols, 2,4,6-triiodophenol, l-hydroxy-2,4-dibromonapthaline andS-hydroxy-S,7-dibromoquinoline.

10. Improved process claimed in claim 1, wherein said triazine reactantis a member selected from the group consisting of cyanuric chloride,2anilido-4,6- dichloro-s-triazine,2,4-di-(diethylamino)-6-chloro-striazine,2-n-butyl-amino-4,G-dichloro-s-triazine, 2-cyclohexylamino-4,fi-dichloro-s-triazine, 2-noctylamino-4,6-dichloro-s-triazine, 2-mopholino-4,6- dichloro-striazine, 2-ethoxy-ethylamino-2,4-dichloros-triazine,2-piperidino-2,4-dichloro-s-triazine and 2-0-napthylamino-2,4-dichloro-s-triazine.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 682908 Dated gust 8 1972 Inventor(s) Roshdy Ismail It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 1, line 61, C H should be inserted before "chlorides". Column 4,line 51, "esters" should read ethers H Column 7, line 38, s--- should beinserted following "6*ch1oro-". Column 9, line 2, "Ncdi" should read HN,N-di

Signed and sealed this 29th day of May 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents USCOMM-DC 5037 5-P69 FORM PC4050 (10-69) u.s GOVERNMENTPRINTING omcz: Isis 036633l.

2. The improved process claimed in claim 1, carried out at a temperatureof about 80* to 200* C.
 3. Improved process claimed in claim 1, carriedout at pressure of about atmospheric to about 12 atmospheres gauge. 4.Improved process claimed in claim 1, wherein said catalyst is present ina proportion of about 0.1 to 2 mol percent.
 5. Improved process claimedin claim 1, wherein said reaction is carried out in a solvent. 6.Improved process claimed in claim 1, wherein said reaction is carriedout in the melt.
 7. Improved process claimed in claim 5, wherein saidsolvent is a member of the group consisting of isoactane fractionshaving a boiling range of about 120* to 200* C, benzene fractions havinga boiling range of about 120* to 200* C benzene, toluene, xylene,o-dichlorobenzene, nitrobenzene, diisopropylether, diisoamylether,dimethylether of ethylene glycol, dimethyl ether of diethylene glycol,diphenyl ether 1,4 dioxane, dimethyl sulfoxide and dimethyl formamide.8. Improved process claimed in claim 1, wherein said halogenated phenolis monohydric.
 9. Improved process claimed in claim 1, wherein saidhalogenated phenol is a member selected from the group consisting of4-fluorophenol, pentafluorophenol, 2-chlorophenols, 3-chlorophenols,4-chlorophenols, 2,3-dichlorophenols, 2,4-dichlorophenols,2,5-dichlorophenols, 2,6-dichlorophenols, 3,4-di-chlorophenols,3,5-dichlorophenols, 2,4-dichloro-6methylphenol,2,6-dichloro-4-tert.-butylphenol, 2,3,5-trichlorophenols,2,4,5-trichlorophenols, 2,4,6-trichlorophenols,2,3,4,6-tetrachlorophenol, pentachlorophenol, 2-bromophenols,3-bromophenols, 4-bromophenols, 2,4-dibromophenols, 2,6-dibromophenols,2,4,6-tribromophenol, pentabromophenol, 2,4-diiodophenols,2,6-diiodophenols, 2,4,6-triiodophenol, 1-hydroxy-2,4-dibromonapthalineand 8-hydroxy-5,7-dibromoquinoline.
 10. Improved process claimed inclaim 1, wherein said triazine reactant is a member selected from thegroup consisting of cyanuric chloride,2-anilido-4,6-dichloro-s-triazine,2,4-di-(diethylamino)-6-chloro-s-triazine,2-n-butyl-amino-4,6-dichloro-s-triazine,2-cyclohexylamino-4,6-dichloro-s-triazine,2-n-octylamino-4,6-dichloro-s-triazine,2-mopholino-4,6-dichloro-s-triazine,2-ethoxy-ethylamino-2,4-dichloro-s-triazine,2-piperidino-2,4-dichloro-s-triazine and 2- Alpha -napthylamino-2,4-dichloro-s-triazine.